Rotational transitions of N2(a 1Πg) induced by collisions with Ar/He and N2(a 1Πg)–N2(X 1Σ+g) rovibronic energy transfer studied by laser REMPI spectroscopy

This paper reports the results of two related experiments: (A) The state-to-state rotational transition probabilities of N2(a 1Πg) in collisions with rare gas atoms (Ar or He) were measured by the technique of two-step multiphoton ionization. Results show that the selection rule antisymmetric–symmetric is obeyed. The transition probability drops rapidly with increasing ‖ΔJ‖. A propensity rule related to the Π+ or Π− symmetry conservation of the electronic wave function during the collision induced rotational transition holds. (B) The cross section for the rovibronic energy transfer between N2(1Πg) and N2(X 1Σ+g) is found to be ∼28 Å2. N2(a 1Πg) product populations show a Boltzmann-like distribution with a rotational temperature suggesting an equipartition of the available energy among the rotational and translational degrees of freedom of the products. A mechanism invoking an intermediate collision complex along with intermolecular electron exchange may explain the results.